Dynamic Raman Line Shapes on an Evolving Excited-State Landscape: Insights from Tunable Femtosecond Stimulated Raman Spectroscopy.

Tracking molecular motions in real time remains a formidable challenge in science and engineering fields because the experimental methodology requires simultaneously high spatial and temporal resolutions. Building on early successes and future potential of femtosecond stimulated Raman spectroscopy (FSRS) as a structural dynamics technique, we present a comprehensive study of stimulated Raman line shapes of a photosensitive molecule in solution with tunable Raman pump and probe pulses. Following femtosecond 400 nm electronic excitation, the model photoacid pyranine exhibits dynamic and mode-dependent Raman line shapes when the Raman pump is tuned from the red side toward and across the excited-state absorption (ESA) band (e.g., from S) with varying resonance conditions. On the anti-Stokes FSRS side, low-frequency modes below ∼1000 cm exhibit a line shape change from gain to dispersive to loss, whereas the dispersive intermediate is much less notable for high-frequency modes. The characteristic mode frequency blue shift involving vibrationally hot states in S with time constants of ∼9.6 and 58.6 ps reveals the sensitivity of anti-Stokes FSRS to vibrational cooling and solvation. This work lays the foundation for expanding tunable FSRS technology on both the Stokes and anti-Stokes sides to investigate a variety of photoinduced processes in solution with sufficient resolution to expose functional motions and increased sensitivity to monitor vibrational cooling.